Production of aryloxyalkyl halides



Patented May 27, 1 952 i UNITED STATES PATENT OFFICE 2,598,049PRODUCTION OF ARYLOXYALKYL HALIDES William K. T. Gleim, Orland Park,Ill., assignor to Universal Oil Products Company, Chicago, Ill., acorporation of Delaware No Drawing. Application December 30, 1949,Serial No. 136,153

8 Claims. (01. 260-613) 1- 2 This invention relates to aryloxyalkylhalides from the members of the'group, consisting of a and to a'processfOl' producing these compounds. phenyl group, an alkylphenyl group, ahydroxy- More specifically, the process relates to certain phenyl group,a hydroxyalkylphenyl group, an aryloxypropyl chlorides and to a novelmethod alkoxyphenyl group, and an allyloxyphenyl for producing them.group, R2 represents a member of the group con- An object of thisinvention is to produce a sisting 'of a hydrogen atom and an alkylgroup, 1-aryloxy-3-chloroalkane. and X represents a halogen atomselected from Another object of this invention is to produce the membersof the group consisting of bromine a l-aryloxy-B-chloropropane. andchlorine.

A further object of this invention is to produce The aryloxyalkylhalides formed by this process l-phenoxy-2-methy1-3-chloropropane. areuseful as intermediates in the synthesis of One specific embodiment ofthis invention dyes, pharmaceuticals, nonionic detergents, etc. relatesto a process for producing an aryloxy-3- The addition of a hydrogenhalide such as hyhaloalkane which comprises reacting a hydrogen drogenbromide or hydrogen chloride to an arylhalide selected from the groupconsisting of hyl5 oxyallyl ether may be carried out in acetic aciddrogen chloride and hydrogen bromide in the 7 solution at a temperatureof from about -50 to presence of an antioxidant with an organic comabout+50 C. and preferably at a temperature pound represented by the formulaof from about to about +25 C. The process RO GH2 C=CH, may be carriedout using either batch or con- 1 2o tinuous types of operation afterwhich the resultant reaction products are separated into unin which R1represents a member of t group converted starting material and thedesired hyconsisting of a phenyl group, an alkylphenyl drohalogenatedreaction p uc group, a hydroxyphenyl group, a hydroxyalkyl- The natureof this invention is illustrated furphenyl group, an alkoxyphenyl group,and an 25 ther by the following examples which should not allyloxyphenylgroup, and R2 represents a, membe m1sconstrued to limit unduly thegenerally ber of the group consisting of a hydrogen atom broad scope ofe invention. and an alkyl group.

I have found that in the presence of an anti- Example I oxidant likehydroquinone, eta, hy r Di-B-methallyl ether of hydroquinone wasdismide, or hydrogen chloride, a s o the double solved in glacial aceticacid containing some hybond of an arylallyl eth r in a manner contrarydroquinone and into the resultant solution gasto t t generally expectedI Y found that eous hydrogen chloride was conducted at 20 C. the halo ena o s h as a bromme atom or a Addition of hydrogen chloride to thedouble chlorine atom adds to t e Carbon atom'which bonds of thedimethallylether of hydroquinone is already combined with two hydrogenatoms yielded 1 4 11- 1 2' t 1 d th hydrogen of the hydrogen halid addszene which wasawell crystallized compound havto the other end of thedouble bond, that is, to ing a melting point of 7g. '79 C and a chlorinethe tertiary carbon atom. The result of this unt t of 23.3% by weightwhich was in good expected manner in which the hydrogen halide 4oagreement with a calculated value of 24.4% for adds to an allyl group ofthe above-mentioned t chlorine atoms per molecule compound, is theproduction of an aryloxy-3- w some of t compound and hydroh l namely, acompound con a i a quinone were refluxed together for four hours in pary halogen ato rather than One containthe presence of sodium methylateused as a cataing a tertiary halog a 4.5 lyst to form an ether withhydroquinone, all of Thus the hy halide addition reaction of thestarting material was recovered unchanged. this process n the presenceof an antioxidant This recovery of the unconverted chlorine consuch ashy q YD QL other taining starting material was evidence of the suitablereducing agents, 0-, m y be reprepresence of a primary alkyl chloriderather than sentediby the equation 5o atertiary alkyl chloride.

R2 2 benzene was obtained by reacting hydrogen chloin which R1represents an aryl group selected ride at a temperature of 20-25 c. withth l-methoxy-4- (3-chloro 2'-methyl) -propoxy- This treatment withsilver acetate yielded. 95% v of the acetic acid ester. This'is furtherproof that the chlorine present was attached to a pri mary carbon atomand not to a tertiary carbon atom. Tertiary alcohol estersof aceticacidare not prepared readily by refluxing tertiary alkyl halides with silveracetate. v

I claim as my invention:

1. A process for producing anaryloxy-ii-haloalkane which comprisesreacting a hydrogen halide selected from the group consisting of hydrogen chlorid and hydrogen bromide in the presence of an antioxidantwith an organic compound represented by the formula:

in which R1 represents a member of the group consisting of a phenylgroup, an alkylphenyl group, a hydroxyphenyl group, a hydroxyalkylphenylgroup, an alkoxyphenyl group, and an allyloxyphenyl group, and R2represents a member Of the group consisting of a hydrogen atom and analkyl group.

2. A process for producing an aryloxy-3-chloropropane which comprisesreacting hydrogen chloride and a B-m-ethallyl aryl ether in the presenceof an antioxidant.

3. A process for producing an aryloxy-3-chloropropane which comprisesreacting hydrogen chloride and a fl-methallyl aryl ether in the presenceof a hydroquinone antioxidant.

4. A process for-producing 1,-di(3 -chloro-2- methyl) -propoxybenzenewhich comprises reacting the fi-dimethallyl ether of hydroquinone withhydrogen chloride in the presence of hydroquinone. p

5. A process for "producing 1-methoxy-4-(3-ch1oro.-2'-methyl)-prcpoxybenzene which comprises reacting theB-methallyl ether of p-hydroxyanisole'with hydrogen chloride in thepresenoe or hydroquinone.

6.. 1A di (3'-chloro-2-methyl) -propoxybenzene.

7. l-methoxy 4 (3'-chloro-2'-methyl)-propoxybenzene. f

8. The process as defined in claim 1 further characterized in that saidhydrogen halide and said organic-compound are reacted in the presence ofa hydroquinone antioxidant.

WILLIAM K. T. GLEIM.

REFERENCES CITED The following references are of record in the file ofthis patent:

Coleman et al. May 23, 1939

2. A PROCESS FOR PRODUCING AN ARYLOXY-3-CHLOROPROPANE WHICH COMPRISESREACTING HYDROCARBON CHLORIDE AND A B-METHALLYL ARYL ETHER IN THEPRESENCE OF AN ANTIOXIDANT.